KR100757049B1 - Preparation of cationic surfactant useful for softening or anti-static agent for fibers - Google Patents

Abstract

A method for preparing a cationic surfactant compound without hydrolysis, and a composition containing the compound useful as a fiber softening agent or an antistatic agent are provided to improve water absorption. A method for preparing a cationic surfactant compound comprises the steps of reacting a triglyceride-based fat directly with a tertiary amine for esterification or amidation; and obtaining a quaternary compound from the obtained product to prepare a compound represented by the formula 1 or 2, wherein R1 to R4 are independently a carboxyl group unsubstituted or substituted with a C1-C3 alkyl group, a hydroxyl group or a C12-C22 linear or branched or alkyl or alkenyl group; R5 is -CH2CHNHC(O)R; R is a C12-C22 linear or branched alkyl or alkenyl group; and X is a halogen atom or an alkyl sulfonate group.

Description

Preparation method of cationic surfactant useful as textile emulsion or antistatic agent {PREPARATION OF CATIONIC SURFACTANT USEFUL FOR SOFTENING OR ANTI-STATIC AGENT FOR FIBERS}

The present invention relates to a novel method for synthesizing cationic surfactants useful as emulsions or antistatic agents for textiles and to emulsions or antistatic agents for apparel and textiles comprising the surfactants.

Cationic surfactants are those in which the hydrophilic group dissociates into cations when dissolved in water, and these cationic surfactants exhibit normal surfactant effects such as washing, emulsifying, and solubilizing, and also have softening or antistatic effects. From the structural features are classified into quaternary ammonium salts and amine derivatives.

Cationic dialkyldimethylammonium salts (JAOCS 61, 367 (1984) and JAOCS 65 (10), 1682 (1988)) have been used for a long time as the main components of the classic fiber emulsion and antistatic agent. However, dialkyldimethylammonium salts have low biodegradability, and cationic surfactants containing functional groups capable of biodegradation, such as ester groups, have been developed and used.

Synthesis of compounds incorporating an ester compound into the molecule has been a very advanced development in terms of environment. As a representative example, in WO 94/07978, a quaternized cationic surfactant derived from triethanolamine is used as a textile emulsion and a hair cleaning product. Application was made and WO 92/15745 discloses the application of imidazoline esters. In Japanese Patent No. 6-336466, there is an example of synthesis and application of amido ester amine compounds. However, all of the above patents are common in that they are based on various amines and fatty acids.

As such, the synthesis of ester cationic surfactants generally involves first reaction with fatty acids, amines and tertiary agents, followed by the use of acids in the quaternization step, quaternary salts of ester based quaternary salts, amido ester amines or already. Dazoline ester quaternary salts are obtained.

However, this synthetic process using fatty acids requires a process that must hydrolyze the fat or oil of the triglyceride form, which is the starting material of fatty acids, and is constrained by the inefficiency of the process and the inability to use various oils and fats.

 The fatty acids that are currently industrialized are hydrolyzed products such as tallow, palm and soybeans, and rarely canola oil or sunflower seed fatty acids are commercialized. However, thanks to the recent well-being craze, various oil and fat applications such as green tea oil, grape seed oil, cotton seed oil, olive oil, peanut oil and safflower seed oil are required.

In order to solve this problem, the present inventors have developed a process for directly cationizing fats and oils.

According to the present invention, a fatty acid amine containing glycerin was prepared by directly reacting fats and oils with an amine, and the reaction process was simplified by introducing a method of performing a quaternization reaction by reacting with a quaternizing agent or neutralizing with an acid. In this case, the glycerin produced in the reaction process improves the antistatic and water dispersing capacity while reducing the amount of solvent used to assist the reaction. In the present invention, various oils applicable to omission of the process required for fatty acid can be directly used for the synthesis of cationic surfactants, which can be usefully used for the development of fiber emulsions or antistatic agents.

In order to achieve the above object, in the present invention, cationic, comprising directly reacting a fat or oil in the form of triglycerides with a tertiary amine, esterifying or amidating the fat or oil, and quaternizing the product obtained in the step. Provided is a process for preparing a compound of formula 1 or formula 2 as a surfactant:

Where

R ₁ , R ₂ , R ₃ and R ₄ are each unsubstituted or substituted with a carboxyl group substituted with alkyl, hydroxy alkyl having 1 to 3 carbon atoms, or a straight or branched alkyl or alkenyl group having 12 to 22 carbon atoms, Or a combination thereof, R ₅ is —CH ₂ CH ₂ NHC (O) R, wherein R is a straight or branched alkyl or alkenyl group having 12 to ₂₂ carbon atoms, and X is halogen or alkylsulfonate.

Hereinafter, the present invention will be described in more detail.

As described in the following scheme, the process for preparing the quaternized ammonium or imidazolium ester derivatives of formula (I) or formula (II) according to the present invention is carried out using the first reaction step, esterification or amidation reaction and quaternizing agent. The treatment consists of two stages of the quaternization reaction, which is characterized in that the oil or fat is directly used in the esterification or amidation reaction of the first stage.

The oils and fats that can be used in the present invention include palm oil, soybean oil, palm oil, canola oil, sunflower seed oil and the like, green tea oil, grape seed oil, cotton seed oil, olive oil, peanut oil, safflower seed oil, rapeseed oil, and the like. no.

First, the present invention is a quaternary ammonium having the structure of Formula 1 by reacting fats and oils with hydroxyalkyl group-containing tertiary amines such as triethanolamine or methyldiethanolamine, and then quaternizing as shown in Scheme 1 below. Ester can be prepared.

In the above scheme, R ₁ , R ₂ , and R ₃ are as defined above, R is a straight or branched alkyl or alkenyl group having 12 to 22 carbon atoms, and R ₆ is OH or straight chain having 12 to 22 carbon atoms. Or a branched alkyl group, alkenyl group, or a group of one or more thereof mixed together.

Specifically, the first step in the reaction of Scheme 1 is the reaction of fats and oils and hydroxyalkyl group-containing tertiary amines such as triethanolamine and methyldiethanolamine, whereby mono-, di-, and tri-ester compounds are prepared by this reaction. Higher diester content is advantageous.

The amount of the fat or oil used in the reaction is preferably in the range of 0.45 to 0.75 equivalents of the amine used.

In the reaction, glycerol, monoglyceride, diglyceride, triglyceride, and the like may be produced as reaction by-products, and their contents are determined by reaction temperature, reaction catalyst, and the like.

In the reaction, NaOH, KOH, Na ₂ CO ₃ , NaBH ₄ , p-TSA (p-toluenesulfonic acid), HCl, H ₂ SO ₄ , H ₃ PO ₂ , and the like may be used as the catalyst. It may range from 0.001 to 0.5% by weight based on the total amount of amines.

The reaction can proceed without solvent, the reaction temperature is in the range of 60 ~ 180 ℃ and the reaction time can be in the range of 1 to 5 hours.

The second step of the reaction scheme 1 is a step in which a quaternization reaction is carried out after adding a solvent after the esterification reaction, in which case ethanol, propyl alcohol, hexylene glycol, butyl alcohol, isopropyl alcohol, ethylene glycol , Primary, secondary, tertiary or polyhydric alcohols such as glycerin, propylene glycol and polyethylene glycol may be used in the form of one kind or a mixture of two or more kinds thereof, and the amount thereof is preferably 30% by weight or less of the total amount of the reactants. Do.

The quaternization reaction may use a known quaternization agent such as CH ₃ Cl, (CH ₃ ) ₂ SO ₄ , (CH ₃ CH ₂ ) ₂ SO _4, HCl as the quaternizing agent, when using dimethyl sulfate For example, dimethyl sulfate uses 0.8-1.0 equivalent of the amine used, reaction temperature is 40-80 degreeC, and reaction time is 1.0-5.0 hours.

Further, according to the present invention, for example, a quaternary imidazolyl having the structure of Chemical Formula 2 by cyclization of a fat and oil and diethylenetriamine by a process such as the following Scheme 2 and quaternization using a quaternizing agent It is possible to prepare the nium salt.

In the above scheme, R, R ₄ , R ₅ , and R ₆ are as defined above.

Specifically, the first step is a reaction that induces a cyclization reaction while removing water by reaction of a fat and amine such as diethylenetriamine.

At this time, it is suitable that oils and fats use the range of 0.65-0.70 equivalent of tertiary amine. At this time, the side reaction may produce dialkylamidopropylamine which is not cyclized, and as a reaction by-product, glycerol, monoglyceride, diglyceride, triglyceride, etc. may be produced. And so on.

As a catalyst that may be used in the reaction, NaOH, KOH, Na ₂ CO ₃ , NaBH ₄ , p-TSA, HCl, H ₂ SO ₄ , H ₃ PO ₂ , and the like may be used. It may range from 0.001 to 0.5% by weight based on the range.

The reaction can proceed without solvent, the reaction temperature is 100 ~ 200 ℃ and the reaction time can range from 3 to 8 hours.

The reaction of the second step may be carried out in the same manner as in Scheme 1 by adding a solvent after the cyclization reaction.

The cationic surfactant prepared according to the present invention can be applied as an apparel, textile emulsion and antistatic agent. The compound of Formula 1 and the compound of Formula 2 according to the present invention may be used singly or as appropriately mixed.

When the compounds of Formula 1 and Formula 2 are directly used as an emulsion for fibers or clothing or for the purpose of antistatic purposes, the final use concentration may be 0.0001% to 10% per 1 liter of water, or in parallel, at this concentration. The use of these concentrations can be encouraged by direct use or by intermediate production with a fiber emulsion or antistatic agent.

At this time, if the use concentration is too low or less than 0.0001%, it is difficult for the compound to have an interfacial action, and at a high concentration of 10% or more, since the concentration exceeds the adsorption concentration on the surface of the object to be treated, loss (loss) is meaningless.

When commercializing the compound, it may further comprise a conventional nonionic surfactant as an emulsifier if necessary. Such nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkenyl ethers or polyoxyethylene alkyl phenyl ethers having 10 to 20 carbon atoms; Alkyl hydroxy fatty acid esters having 10 to 20 carbon atoms; Sorbitan fatty acid alkyl esters and ethylene oxide adducts thereof, and polyoxyethylene alkyl amides, polyoxyethylene alkenylamides; Polyoxyethylene alkylamines, polyoxyethylene alkenylamines; Glyceryl monoalkyl alkenyl esters; Ethylene oxide adducts of hardened castor oil; Alkylamine oxides; Or amidopropylamine oxide or the like may be used alone or in combination of two or more thereof, but is not limited thereto, and is preferably used within 0.1 to 5% by weight of the total content.

In addition, the fabric softener or antistatic agent composition of the present invention may be used as a stabilizer of lower alcohol or glycols having 1 to 8 carbon atoms, higher alcohols having 12 to 20 carbon atoms, urea, magnesium chloride, sodium chloride, calcium chloride or sodium nitrate, etc. In addition, additives such as fragrances, preservatives, fungicides, fluorescent brighteners, pigments, antioxidants, or antifoaming agents may be further included.

Hereinafter, preferred embodiments are presented to help understand the present invention. However, the following examples are provided only to more easily understand the present invention, and the present invention is not limited to the following examples.

<Example 1>

In a four-necked flask equipped with a mechanical stirrer, a thermometer, a condenser, and a distillation apparatus, 452 g of palm oil and 149 g of triethanolamine were added under a nitrogen atmosphere, and 0.5 g of KOH was added thereto, followed by esterification at 150 ° C. for 4 hours. The acid value was 3 or less after the reaction was completed.

After the reaction product was cooled, 130 g of a solvent (IPA / EtOH = 4/11) was added thereto, and 118 g of dimethyl sulfate was slowly added dropwise while maintaining the temperature at 55 ° C. or lower. After the addition was completed, the reaction was performed at 60 ° C. for 2 hours, and then the reaction was terminated.

The obtained compound contained about 15% of mono, di, glyceride and glycerin, and about 15% of IPA / EtOH solvent, and yielded about 70% of dialkylhydroxyethyl methyl sulfate.

<Example 2>

In the same device as in <Example 1>, palm oil 565g and 103g of diethylenetriamine were added thereto, 0.3 g of NaBH ₄ was added thereto, and the amidation reaction was performed at 150 ° C. for 5 hours at atmospheric pressure. The reaction was carried out for a time to proceed with the cyclization reaction. At this time, the acid value was 1 or less and the cyclized compound was obtained in a yield of 90% or more.

After cooling the cyclized compound, 200 g of a solvent (EtOH) was added thereto, and 121 g of dimethyl sulfate was slowly added dropwise while maintaining the temperature at 55 ° C or lower. After the addition was completed, the reaction was performed at 60 ° C. for 2 hours, and then the reaction was terminated.

The obtained compound contained about 15% of mono, di, glyceride and glycerin, and about 15% of EtOH solvent, and yielded about 70% of dialkyl imidazolinium methyl sulfate.

Comparative Example 1

In a four-necked flask equipped with a mechanical stirrer, a thermometer, a condenser, and a distillation apparatus, 230 g of industrial stearic acid and 214 g of industrial oleic acid were mixed under a nitrogen atmosphere to remove 149 g of triethanolamine and 190 ° C at atmospheric pressure for 6 hours. During the ester reaction. The acid value was 2 or less after the reaction was completed.

After the reaction product was cooled, 130 g of a solvent (IPA / EtOH = 4/11) was added thereto, and 119 g of dimethyl sulfate was slowly added dropwise while maintaining the temperature at 55 ° C. or lower. After the addition was completed, the reaction was performed at 55 ° C. for 5 hours, and then the reaction was terminated.

The obtained compound contained about 15% of IPA / EtOH solvent and yielded about 85% of dialkylhydroxyethyl methyl sulfate.

Comparative Example 2

In the same apparatus as in <Comparative Example 1>, 540 g of palm oil and 102 g of diethylenetriamine were added thereto, 0.3 g of NaBH ₄ was added thereto, and the amidation reaction was performed at 150 ° C. for 5 hours at atmospheric pressure. The reaction was carried out for a time to proceed with the cyclization reaction. At this time, the acid value was 1 or less and the cyclized compound was obtained in a yield of 88% or more.

After cooling the cyclized compound, 200 g of a solvent (EtOH) was added thereto, and 120 g of dimethyl sulfate was slowly added dropwise while maintaining the temperature at 55 ° C or lower. After the addition was completed, the reaction was performed at 60 ° C. for 2 hours, and then the reaction was terminated.

The obtained compound was able to obtain dialkyl imidazolinium methyl sulfate having a yield of about 75% containing about 25% of EtOH solvent.

Stability test

The stability test was performed on the compounds synthesized in the above <Example 1>, <Example 2>, <Comparative Example 1> and <Comparative Example 2> as follows.

Specifically, the synthesized compound samples were put in 200ml test containers, respectively, and storage stability was evaluated in a 40 ° C and 50 ° C thermostat. The stability was evaluated by the criteria according to Table 1 below, the results are shown in Table 2 below.

As shown in Table 2, the quaternary ammonium salt surfactants (Examples 1 and 2) of the present invention prepared using oils and fats as starting materials were compared with materials (Comparative Examples 1 and 2) prepared by the fatty acid starting material method. The color stability was slightly lower at high temperature, but it did not affect the quality of the product and the phase stability at high temperature was similarly excellent.

Flexibility, antistatic and absorbency test

<Test Examples 1 and 2>

The test cotton cloth was soaked for 10 minutes in a solution containing 0.1% dilution of the compound prepared in Example 1 and Example 2, and dried.

<Test Examples 3 and 4>

Fabric softeners for clothes using 6% of the compounds prepared in <Example 1> and <Example 2> were prepared, 40 g of the fabric softener was added to 60 L of wash water, and each test cotton garment was rinsed once and dried.

<Test Examples 5 and 6>

A fabric softener for garments using 18% of the compound prepared in <Example 1> and <Example 2> was prepared. At this time, 1% of Oleyleth-20 (manufactured by Uniquea), 2% of m-EG (Honam Petrochemical), and 0.05% of CaCl ₂ were added to aid the emulsification of the cationic surfactant. After the addition, the test cotton garments were rinsed once and dried.

<Test Example 7>

The test cotton cloth was dipped in a solution containing 0.03% of the compound prepared in <Example 1> and 0.02% of the compound prepared in <Example 2> as a diluent for 10 minutes, and then dried.

<Test Example 8>

A fabric softener for clothes using 20% of the compound prepared in Example 1 and 10% of the compound prepared in Example 2 was prepared. At this time, 2% Oleyleth-20 (manufactured by Uniquema), 3% m-EG (Honam Petrochemical), and 0.08% CaCl ₂ were added to aid the emulsification of the cationic surfactant. After the addition, the test cotton clothing was rinsed once and dried.

Comparative Test Example 1

The compound prepared in <Comparative Example 1> was dipped in a solution containing 0.7% dilution for 10 minutes and dried.

Comparative Test Example 2

A fabric softener for clothes using 6% of the compound prepared in <Comparative Example 1> was prepared, 40 g of a fabric softener was added to 60 L of wash water, and the test cotton clothing was rinsed once and dried.

Comparative Test Example 3

A fabric softener for garments using 18% of the compound prepared in <Comparative Example 1> was prepared. At this time, 1% of Oleyleth-20 (manufactured by Uniquea), 2% of m-EG (Honam Petrochemical), and 0.05% of CaCl ₂ were added to aid the emulsification of the cationic surfactant. After the addition, the test cotton clothing was rinsed once and dried.

Comparative Test Example 4

The test cotton cloth was dipped in a solution containing 0.03% of the compound prepared in Comparative Example 1 and 0.02% of the compound prepared in Comparative Example 2 as a diluent, followed by drying for 10 minutes.

Comparative Test Example 5

A fabric softener for garments using 12% compound prepared in Comparative Example 1 and 6% compound prepared in Comparative Example 2 was prepared. At this time, 1% Oleyleth-20 (manufactured by Uniquea), 2% m-EG (Honam Petrochemical), and 0.05% CaCl ₂ were added to aid the emulsification of the cationic surfactant. After the addition, the test cotton clothing was rinsed once and dried.

The test cloth or rinse solution obtained in the above <Test Example> and <Comparative Test Example> was tested for flexibility, antistatic property and water absorption, and each test method was as follows.

1) flexibility

The treated test cloths were evaluated by 10 experienced subjects based on the control sample as follows and the average value was treated as a flexible value. As a control sample, a test cloth of <Comparative Test Example 2> was used.

+2: Very flexible compared to the control sample

+1: slightly more flexible than the control sample

0: equivalent to control sample

+1: slightly inferior to the control sample

+2: Very poor flexibility compared to the control sample

2) Antistatic

The standard white cloth, white polyester cloth and nylon cloth (manufactured by Korea Apparel Testing Institute) of KS K 0905 were washed with a general laundry detergent, and then naturally dried and cut into 5 × 5 cm sizes, respectively. Into the composition according to the Examples and Comparative Test Examples (1% aqueous solution based on pure substances, 20 ℃) and treated for 3 minutes and then air-dried, and 20 ± 2 ℃, 65 ± 3% RH or 40 ± 3% RH for 24 hours After conditioning under constant temperature and humidity conditions, the half-life was measured as the leakage rate of the static charge of each sample when the initial constant voltage of 150 volts was applied by the KS K 0555C test method using the Swiss Voltchild Static Voltmeter. Was in accordance with the criteria of Table 3 below.

3) absorbency

The test fabric treated in each test example was cut to a length of 3 cm × 20 cm and dipped 2 cm at the tip into an aqueous solution in which a water-soluble dye was diluted, and then stood using a support. After 15 minutes for each sample the height raised in the aqueous dye solution is measured.

The flexibility, antistatic and absorbency test results are shown in Table 4 below.

As shown in Table 4, the fiber emulsion and the antistatic agent composition using the compound according to the present invention are the same within the significant difference in flexibility and the compound-containing composition according to the conventional method, the antistatic ability is the same, the absorption is rather Appeared excellent.

Quaternary ammonium or imidazolium compounds prepared in accordance with the present invention and fibrous emulsions using the compounds, antistatic agents have the advantages of low process cost, various oil and fat applications, and are similar to compounds prepared using conventional fatty acids. Indicates quality.

Claims (8)

Reacting the fat or oil in the form of triglycerides directly with a tertiary amine to esterify or amidate the fat or oil, and to quaternizing the product obtained in the step. Preparation of the compound of 2: <Formula 1>

<Formula 2>

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each unsubstituted or substituted with alkyl, hydroxy alkyl having 1 to 3 carbon atoms, or a straight or branched alkyl or alkenyl group having 12 to 22 carbon atoms. Carboxyl group, or a combination thereof, R ₅ is —CH ₂ CH ₂ NHC (O) R wherein R is a straight or branched alkyl or alkenyl group having 12-22 carbon atoms, X is halogen, or alkylsulfo Nate. The method of claim 1, Tertiary amine is selected from the group consisting of triethanolamine, dimethylethanolamine, diethylenetriamine and the like. The method of claim 1, A fat or oil is used in the range of 0.45 to 0.75 equivalents of the tertiary amine. The method of claim 1, In the esterification or amidation reaction, a catalyst selected from the group consisting of NaOH, KOH, Na ₂ CO ₃ , NaBH ₄ , p-toluene sulfonic acid, HCl, H ₂ SO ₄ , and H ₃ PO ₂ is used. How to. The method of claim 4, wherein Wherein the catalyst is used in an amount ranging from 0.001 to 0.5% by weight based on the total amount of fats and oils and amines. The method of claim 3, wherein Characterized in that the esterification reaction is carried out at 60 to 180 ° C. for 1 to 5 hours. The method of claim 1, A fat or oil is at least one selected from the group consisting of palm oil, soybean oil, palm oil, canola oil, sunflower seed oil, green tea oil, grape seed oil, cotton seed oil, olive oil, peanut oil, safflower seed oil, and rapeseed oil. An emulsion for clothing or textiles comprising a compound of formula 1 or formula 2 according to any one of claims 1 to 7 together with any other surfactant at a concentration of 0.0001% to 10% per liter of water or Antistatic agent composition.